Method of stabilizing regenerated cellulose textiles with aldoketene dimers and textile hand-modifying agents and products resulting therefrom



Unite States Paten t NIETHOD OF STABILIZING REGENERATED CELLULOSE TEXTILES WITH ALDOKETENE DIIVIERS AND TEXTILE HAND-MODIFYING AGENTS AND PRUDUCTS RESULTING THEREFROM Joseph A. Cafasso, Providence, R. I., assignor to Anterican Viscose Corporation, Philadelphia, Pa., a corporation of Delaware No Drawing. Application November 10, 1953, Serial No. 391,370

13 Claims. (Cl. 8115.6)

The present invention relates to stabilized regenerated cellulose textile materials and to methods of producing them.

The term textile material is intended to include continuous filaments and staple fibers or yarns formed thereof, whether in the finished stage or at an intermediate stage in their production, as well as fabrics made from such yarns, whether knitted, woven, or felted, garments, so-called non-woven fabrics, and other fibrous articles.

The novel features of the invention are of special importance as applied to fabrics made of yarns formed from or comprising fibers or filaments of regenerated cellulose, including those predominantly of spun viscose rayon, and the invention will be discussed more in detail in connection with such application.

By stabilization is meant the rendering of the textile material, such as a woven fabric, resistant to progressive dimensional shrinkage on laundering or washing.

While the primary object of the. present invention is to stabilize textile materials of regenerated cellulose, ancillary objects are to provide along with such stabilization an improved resistance to rupturing by tearing or flexing actions. It is also an ancillary object to provide a stabilization treatment which is adapted to imp-art softmess to the fabric or various degrees of stiffness or firmness. Other objects and advantages will be apparent from the description thereof hereinafter.

The objects of the present invention are accomplished by reacting the regenerated cellulose textile material with a dimer of a higher aliphatic ketene, more accurately termed an aldoketene corresponding to the formula R.CH= C=O, having 10 to 20 carbon atoms. Such dimers are at present generally considered to have the following formula:

RCH=C-CHR are.)

in which R is an alkyl or alkylene group having 8 to 18 carbon atoms. For example, R may be octyl, capryl, lauryl, myristyl, hexadecyl, oleyl or octadecyl.

The nature of the reaction product of the cellulose is not positively known but it is believed to be either an ester having a formula as follows:

in which R is the same as above and n may be any fractional, integral, or mixed number or the resulting product may possibly be an acetal having the formula in which R is the same as above, n is the same as above and m may be an integral number from 1 to 2, and Cell represents the residue of a cellulose molecule. The latter acetal structure includes the possibility of producing crosslinked molecules. However, whether such reaction prod- 2,791,484 Fatented May 7, 1957 ucts or others are formed, it has been found that the products obtained in accordance with the process hereinafter outlined are rendered stable against dimensional shrinkage on laundering and they are unusually resistant to the removal of the dimer residues by hydrolytic action, particularly in alkaline medium. Hence, the products can be scoured under severe alkaline conditions without suffering loss of their stabilized character.

In order to bring about the stabilization, the dimer is emulsified in an aqueous medium by means of a suitable emulsifier and an acidic catalyst is introduced to provide a pH in the emulsion between 1.0 and 2.0, preferably 1.2 to 1.4. The textile material is impregnated with such emulsion, such as by passing the material through a bath of the emulsion or by spraying the emulsion upon the material or by transferring the emulsion by means of rollers, wicks or the like to a travelling length of the textile material.

Any acid-stable emulsifier may be used. Preferably, non-ionic emulsifiers, such as ethylene oxide derivatives of partial esters of polyhydric alcohols, such as glycerine, sorbitol, mannitol, or inner ethers thereof with. higher fatty acids may be used. For example, sorbitan monopalmitate, polyoxyethylene derivatives of sorbitan monopalmitate, polyoxyethylene derivatives or rosin, or of hydroabietyl alcohol or of glycerine may be used. The proportion of dimer in the emulsion may be from 2 to 10% by weight, preferably about 4 to 6%. Approximately one part by weight of the emulsifier is used for each five parts by weight of dimer.

As a catalyst, any acid or acid salt may be used which is capable of bringing the pH of the emulsion Within the range of 2.0 to 1.0. Acids, such as sulfuric acid, hydrochloric acid, oxalic, maleic, and sulfamic acids may be used. Similarly, acid salts, such as sodium bisulfate may be used. When strong acids, such as sulfuric, hydrochloric or other mineral acid are used or acid salts thereof, such as sodium bisulfate are used, it is perferable to include within the medium, a buffer to prevent tendering or degr'adation of the regenerated cellulose. Buffers, such as sodium sulfate, trisodium phosphate, disodium phosphate or monosodium phosphate, sodium citrate and so forth may be use. The proportion of acid may be from less than 1% up to 2% or more depending upon its strength, the amount being selected to give the desired pH within the range stated hereinabove. Similarly, the amount of buffer may vary from less than 1%, such as from /2 to 2%, again in dependence upon the pH desired.

Optionally, a hand-modifying agent may be included within the emulsion. This agent may consist of a watersoluble cellulose ether, such as methyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, or the like, polyvinyl alcohol, starch, or it may comprise a polymeric material of resinous character which can be dispersed Within the acid emulsion, such as acid-stable thermoplastic emulsions, especially those of polyvinyl acetate. Generally, when such modifier is used, the proportion may be from 1 to 4% by weight within theemulsion, the higher the proportion thereof, the firmer the hand obtained.

The textile material may have the emulsion applied to it at room temperature after which excess is removed and the material is dried, such as at 240 to 250 P. Then the dried material is baked at a temperature to 300 to 350 for a period of time of one to seven minutes, the time being inversely proportional to the temperature selected for the operation. If the material happens to be a fabric, particularly a woven fabric, it is preferred to support the fabric in a somewhat tensioned condition during the application of the emulsion and during the drying. For example, the tension during application of the emulsion may be such as to distend the fabric to increase it from 1 to 6% in either or both the warp and filling directions. During the drying and the curing, the tension may be such as to impart from 1 to 2% greater width (filling direction) and from 1 to 6% greater length (warp direction).

After the baking operation, the textile material is scoured to remove residual salts or acids and this may be accomplished in any aqueous detergent solution, such as a soap solution, a solution of soda ash, or synthetic detergents such as sodium N-methyl-N-oleoyl taurate, or mixtures thereof. The scouring may be performed at temperatures of 120 to 212 F. for a period of two to ten minutes, a preferred operation being carried out at 120 F. for about ten minutes. After the scouring operation, the textile material is dried under relaxed conditions. Then it may be steamed and finally dried in a condition such that the warp is relaxed and the width is about 1 to 2% greater than that after the immediately preceding drying under relaxed conditions. This steaming operation serves to remove any wrinkles that may be introduced by the drying under relaxed conditions.

The resulting textile material is stabilized against shrinkage during repeated washings and in the examples hereinafter, the wash test referred to is that of the Federal Specification CCC-T-191A Cotton Wash Test which involves boiling one hour in soap solution of a concentration of about /2 to 1% on the weight of the goods. The soap used herein was essentially sodium oleate.

In the following examples, the parts given are by weight unless otherwise specified.

Example I An emulsion was produced containing per 1200 cc. of the emulsion, 50 grams of hexadecyl ketene dimer, 10 grams of the ethylene oxide ether of a sorbitan monooleate containing 5 ethylene oxide units per mole, 24 grams of sodium bisulfate and 6 grams of sodium sulfate by mixing the dimer and the emulsifier thoroughly while heating on a steam bath and then stirring in thoroughly 150 cc. of hot water to form an emulsion which emulsion was then added to 300 cc. of water and then diluted to 800 cc. of water. The sodium bisulfate was then dissolved in 150 cc. water and added to the diluted emulsion and then the sodium sulfate was dissolved in 100 cc. of water and added after which the volume was adjusted by the addition of water. The resulting emulsion had a pH of 1.3. A woven textile fabric of challis construction whose filling and warp yarns consisted of spun viscose regenerated cellulose was passed through the emulsion in a pad and an auxiliary box associated therewith. After removal of excess by means of squeeze rolls, it was dried at 240 F. for three minutes under slight tension. It was then cured at 300 F. for five minutes under slight tension. It was scoured for ten minutes at 120 F. in an equeous solution containing 0.5% soda ash and 1.0% sodium N- methyl-N-oleoyl taurate. The fabric was then steamed and dried as described hereinabove and subjected to the Federal Specification CCC-T-l91A Cotton Wash Test with the following results as compared to a control fabric of regenerated cellulose rayon of similar construction which was not treated with the dimer.

An emulsion was prepared as in Example I except that the ketene dimer was replaced with a corresponding amount of the dimer of dodecyl ketene. The resulting fabric showed the following results on washing.

CCC-T-IQIA COTTON WASH TEST Wash: Warp 1st 2.3 2nd 1.8 3rd 2.1 4th l.9 5th 1.8

Example 111 The procedure was the same as in Example I except that there was incorporated into the emulsion a watersoluble hydroxyethyl cellulose ether in an amount of 60 grams per 1200 cc. of the emulsion. The wash tests on the fabric produced the following results:

CCC-T-191A COTTON WASH TEST Wash: Warp change, percent 1st 1.1 2nd 1.1 3rd l 4 4th 1 9 5th -22 Example IV The procedure was as in Example HI except the proportions of dimer and emulsifier were doubled, the proportions of the other ingredients of the emulsion remaining the same. As in Example III, the pH was also 1.3. The results of the wash tests on the fabric were as follows:

CCCT191A COTTON WASH TEST Example V The procedure of Example III was followed except the proportions of dimer and emulsifier were reduced to 20 grams and 4 grams respectively per 1200 cc. of the emulsion. The pH was 1.3 as before and results of the wash tests were as follows:

CCCT-191A COTTO N WASH TEST Wash: Warp change, percent 1st 1.1 2nd 1.1 3rd l.4 4th 1.4 5th 1.1

Example VI An emulsion was prepared containing 4 pounds of hexadecyl ketene dimer, 0.8 pound of the ethylene oxide ether of a sorbitan mono-oleate containing 5 oxyethylene units per mole, 2 pounds of sodium bisulfate and 0.5 pound sodium sulfate in water to make a total of 12 gallons having a pH of 1.3. After padding, the fabric, initially of 36-inch width, was dried in a clip-tenter toa width of thirty-seven and a half inches. It was cured by passing through a pin tenter without overfeed at a temperature of 306 F. for four minutes. Its width was then thirtyseven and a half inches. The fabric was washed in rope form in an aqueous solution containing 1% soda ash and one-fourth percent of sodium N-methyl-N-oleoyl taurate. This scouring was efiected at F. for 15 minutes and was followed by a rinse and a squeeze. The fabric was then dried on a pin tenter with a number 4 overfeed to ,a 36-inch width. It was steamed'and dried on aclip-tenter' to a width of 37 inches. The changes in the measurements or dimensions from that of the initial fabric are summarized as follows:

Warp, Filling,

percent percent Alter padding and drying +11. 7 +3. 3 After curing 1 l 1 1 +10. 8 +3. 3 After washing (scouring) +7. 5 0 After drying +3. 3 0 After steam framing +7.5 +1. 4

The results of the Wash tests were as follows:

CCCT191A COTTON WASH TEST As a comparison of the stability of the fabric to alkaline conditions, a piece of this fabric was introduced along with a piece of a cellulose acetate fabric into an aqueous bath containing 1% caustic soda. The ketenedimer-reacted fabric after boiling in this caustic soda solution for about five minutes (at which time the cellulose acetate was completely saponified to regenerated cellulose and thereby no longer soluble in ether) showed a shrinkage of only 2.5% in the warp whereas an untreated control fabric exhibited a shrinkage of about ten and a half percent.

It is to be understood that changes and variations may be made without departing from the spirit and scope of the invention as defined in the appended claims.

I claim:

1. The method of stabilizing textile materials comprising regenerated cellulose against progressive dimensional shrinkage under repeated washings comprising impregnating said textile material with an aqueous emulsion having a pH of between 1.0 and 2.0 and containing between 2% and by weight, of a dimer of an aldoketene corresponding to the formula RCH=@O wherein R is selected from the group consisting of alkyl and alkylene radicals having from 8 to 18 carbon atoms,

and subsequently baking said impregnated textile ma- 3. The method as defined in claim 1 in which the emulsion contains, as a textile hand-modifying agent, a water-soluble cellulose ether dissolved in the aqueous phase of said emulsion.

4. The method as defined in claim 1 in which the emulsion contains between 4% and 6%, by weight, of said dimer and from 1% to 4%, by weight, of a textile hand-modifying agent.

5. The method as defined in claim 1 in which the emulsion contains between 4% and 6%, by Weight, of said dimer and from 1% to 4%, by weight, of a textile hand-modifying agent composed of a water-soluble hydroxyethyl cellulose.

6. The method as defined in claim 1 in which the dimer is that of hexadecyl ketene.

7. The method as defined in claim 1 in which the dimer is that of dodecyl ketene.

8. The method of stabilizing textile fabrics comprising yarns composed of regenerated cellulose fibers against progressive dimensional shrinkage under repeated washings which comprises impregnating said textile fabric with an aqueous emulsion having a pH of between 1.0 and 2.0 and containing between 2% and 10%, by weight, of a dimer of an aldoketene corresponding to the formula RCH=C=O wherein R is selected from the group consisting of alkyl and alkylene radicals having from 8 to 18 carbon atoms, drying said impregnated textile fabric under tension and subsequently baking said textile fabric at a temperature of from 300 to 350 F. for a period of from 1 minute to 7 minutes.

9. The method as defined in claim 8 in which the dimer is that of hexadecyl ketene and the emulsion also contains, as a textile hand-modifying agent, from 1% to 4%, by weight, of a water-soluble hydroxyethyl cellulose dissolved in the aqueous phase of said emulsion.

10. The method of stabilizing fabrics comprising yarns composed of regenerated cellulose fibers against progressive dimensional shrinkage under repeated washings which comprises impregnating said fabric with an aqueous emulsion having a pH of between 1.0 and 2.0 and containing between 2% and 10%, by weight, of a dimer of an aldoketene corresponding to the formula wherein R is selected from the group consisting of alkyl and alkylene radicals having from 8 to 18 carbon atoms, from about 0.4% to about 2% of an acid stable emulsifier and from about 1% to about 4% of a textile handmodifying agent, drying said impregnated fabric while under tension at a temperature between 240 and 250 F., baking said dried fabric while under tension at a temperature between 300 and 350 F. for a period of from 1 to 7 minutes, scouring said baked fabric and drying said scoured fabric in a relaxed condition.

11. The method as defined in claim 10 in which the dimer is that of hexadecyl ketene.

12. The method as defined in claim 10 in which the dimer is that of dodecyl ketene.

13. As an article of manufacture, a regenerated cellulose textile fabric being resistant to progressive dimen sional shrinkage under repeated washings comprising yarns composed of regenerated cellulose fibers formed by impregnating said fabric with an aqueous emulsion having a pH of between 1.0 and 2.0 and containing between 2% and 10%, by weight, of a dimer of an aldoketene corresponding to the formula R-CH=O=O wherein R is selected from the group consisting of alkyl and alkylene radicals having from 8 to 18 carbon atoms and subsequently baking said impregnated fabric at a temperature of from 300 to 350 F. for a period of from 1 minute to minutes.

References Cited in the file of this patent UNITED STATES PATENTS 2,284,896 Hanford June 2, 1942 2,411,860 Hentrich Dec. 3, 1946 2,436,076 Pfeffer Feb. 17, 1948 2,627,477 Downey Feb. 3, 1953 FOREIGN PATENTS 522,204 Great Britain June 12, 1940 OTHER REFERENCES Adams Organic Reactions, vol. III 1946, pages 127- 132. 

1. THE METHOD OF STABILIZING TEXTILE MATERIALS COMPRISING REGENERATED CELLULOSE AGAINST PROGRESSIVE DIMENSIONAL SHRINKAGE UNDER REPEATED WASHINGS COMPRISING IMPREGNATING SAID TEXTILE MATERIAL WITH AN AQUEOUS EMULSION HAVING A PH OF BETWEEN 1.0 AND 2.0 AND CONTAINING BETWEEN 2% AND 10%, BY WEIGHT, OF A DIMER OF AN ALDOKETENE CORRESPONDING OF THE FORMULA R-CH=C=O WHERE R IS SELECTED FROM THE GROUP CONSISTING OF ALKYL AND ALKYLENE RADICALS HAVING FROM 80 TO 18 CARBON ATOMS, AND SUBSEQUENTLY BAKING SAID IMPREGNATED TEXTILE MATERIAL AT A TEMPERATURE OF FROM 300 TO 350* F. FOR A PERIOD OF FROM 1 MINUTE TO 7 MINUTES.
 2. THE METHOD AS DIFINED IN CLAIM 1 IN WHICH THE EMULSION ALSO CONTAINS A TEXTILE HAND-MODIFYING AGENT.
 13. AS AN ARTICLE OF MANUFACTURE, A REGENERATED CELLULOSE TEXTILE FABRIC BEING RESISTANT TO PROGRESSIVE DIMENSIONAL SHRINKAGE UNDER REPEATED WASHINGS COMPRISING YARNS COMPOSED OF REGENERATED CELLULOSE FIBERS FORMED BY IMPREGNATING SAID FABRIC WITH AN AQUEOUS EMULSION HAVING A PH OF BETWEEN 1.0 AND 2.0 AND CONTAINING BETWEEN 2% AND 10%, BY WEIGHT, OF A DIMER OF AN ALDOKETENE CORRESPONDING TO THE FORMULA R-CH=C=O WHEREIN R IS SELECTED FROM THE GROUP CONSISTING OF ALKYL AND ALKYLENE RADICALS HAVING FROM 8 TO 18 CARBON ATOMS AND SUBSEQUENTLY BAKING SAID IMPREGNATED FABRIC AT A TEMPERATURE OF FROM 300* TO 350* F. FOR A PERIOD OF FROM 1 TO 7 MINUTES. 